硝酸型废退锡水的分离特性与蒸馏强化偏锡酸回收

doi:10.19964/j.issn.1006-4990.2021-0603

Abstract

Abstract:

Aiming at the improvements of regeneration technology and tin extraction mothed of nitric acid type tin stripping waste solution for PCB industries，the physical and chemical characteristics，the behaviors of redox and precipitation reactions，and vacuum distillation characteristics of waste tin stripping solution were theoretically analyzed and experimentally studied.The results showed that Fe³⁺ in nitric acid solution could oxidize tin ion to tetravalent.The increase of nitric acid concentration promoted the precipitation formation of β-type meta stannic acid.Vacuum distillation was the concentration process of nitric acid.When the evaporation rate of water reached 67.75%，the mass ratio of nitric acid increased to 40.04% and the mass ratio of tin decreased to 0.04%.Tin in the waste tin stripping water was precipitated in the form of β-metastannic acid，and the precipitation rate reached 97.36%.The precipitate β-metastannic acid obtained by distillation had better precipitation characteristics.The distillation bottom liquid retained the effective components of tin stripping liquid and could be used to mix tin stripping liquid.

Key words: tin stripped waste liquid, β-metastannic acid, tin stripping solution regeneration, precipitation reaction, vacuum distillation

CLC Number:

TQ134.32

JIN Fenli,ZHA Zhengjiong,WANG Yongcheng,ZHOU Huan. Separation characteristics of nitric acid type tin stripping waste solution and distillation enhanced recovery of meta stannic acid[J]. Inorganic Chemicals Industry, 2022, 54(8): 101-106.

Figures/Tables 12

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References 11

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项目	pH	密度/（g·L^-1）	w（SnO₂）/%	w［Fe（NO₃）₃］/%	w［Cu（NO₃）₂］/%	w（HNO₃）/%	w（H₂O）/%
悬浊液	-0.49	1 368.2	9.763	3.920	1.600	21.318	63.399
澄清液	-0.49	1 190.0	0.948	3.583	1.386	23.617	70.467
湿固相	—	—	33.130	4.810	2.170	15.220	44.660

序号	氧化还原反应	ΔG^{（298 K）}/ （kJ·mol^-1）	反应判断
1	Sn+HNO₃+5H₂O=［Sn（H₂O）₆］²⁺+HNO₂	-186.79	自发
2	［Sn（H₂O）₆］²⁺→［Sn（H₂O）₆］⁴⁺	29.70	不自发
3	Sn²⁺+2HNO₃+2H⁺→Sn⁴⁺+2NO₂+2H₂O	114.67	不自发
4	Cu + HNO₃+H⁺=Cu⁺+ NO₂+H₂O	-27.10	自发
5	Cu⁺+HNO₃+H⁺→Cu²⁺+NO₂+H₂O	-61.57	自发
6	Sn²⁺+2 Cu^{2 +}→Sn⁴⁺+2 Cu⁺	-1.32	自发
7	Fe²⁺+NO₃^-+2H⁺→Fe³⁺+NO₂+H₂O	-1.879	自发
8	Sn²⁺+2Fe³⁺→Sn⁴⁺+2Fe²⁺	-118.70	自发
9	2Sn²⁺+O₂+4H⁺→2Sn⁴⁺+2H₂O	-175.73	自发
10	Sn²⁺+H₂O₂+2H⁺→Sn⁴⁺+2H₂O	-71.40	自发

序号	沉淀反应	ΔG^（298K）/ （kJ·mol^-1）	沉淀终点计算值*（pH）	沉淀终点测定值* 实测pH
11	Sn⁴⁺+2H₂O→SnO₂ +4H⁺	-47.84	>-1.60	—
12	Sn ²⁺+2OH^-→Sn（OH）₂	-149.91	>1.86	1.8
13	Fe³⁺ +3OH^-→Fe（OH）₃	-182.87	>3.98	3.5
14	Cu²⁺ +2OH^-→Cu（OH）₂	-112.20	>5.16	10.0
15	Fe²⁺ +2OH^-→Fe（OH）₂	-93.11	>6.83	—

m（废退锡水）/g	通氧气时间/h	m（H₂O₂）/ g	m（硝酸）/ g	pH	w（Sn⁴⁺）/ %
33.53	3	5	—	-0.66	0.717
33.03	—	—	1.43	-0.66	0.594
32.69	—	—	2.75	-0.71	0.523
32.80	—	—	5.50	-0.75	0.249
32.75	—	—	10.97	-0.85	0.137
32.68	—	—	16.44	-0.91	0.113

溶液质量/g	总蒸失率/%	水蒸出率/ %	pH	w（Sn⁴⁺）/ %	w（Fe³⁺）/ %	w（Cu²⁺）/ %	w（HNO₃）/ %	w（H₂O）/ %	w（馏出液的硝酸）/%	锡的析出率/%
1 005.71	0.00	0.00	-0.66	0.75	1.08	0.71	23.62	68.90	—	0.000
1 005.71	0.00	0.00	-0.55	0.64	1.05	0.74	25.33	67.75	—	0.00
1 030.83	2.02	2.52	-0.56	0.46	1.16	0.80	25.45	67.01	13.86	15.16
932.49	8.82	11.76	-0.57	0.39	1.16	0.81	27.97	64.50	8.21	44.15
933.23	11.43	15.32	-0.58	0.36	1.20	0.81	27.63	64.68	7.59	52.76
906.75	12.50	16.79	-0.59	0.33	1.21	0.82	26.67	65.56	7.43	57.38
894.68	12.40	16.57	-0.60	0.28	1.28	0.85	30.64	61.24	7.88	60.68
849.21	18.61	25.44	-0.61	0.25	1.27	0.83	31.94	60.05	5.82	68.08
856.45	18.99	25.92	-0.62	0.23	1.30	0.87	30.21	61.51	5.95	71.43
833.75	19.72	26.88	-0.63	0.24	1.30	0.88	33.10	58.58	6.08	74.85
832.22	22.38	30.77	-0.65	0.24	1.40	0.90	31.63	59.59	5.28	73.38
776.80	23.91	32.98	-0.68	0.21	1.41	0.93	36.02	55.05	4.96	75.51
766.73	28.26	39.22	-0.71	0.18	1.50	0.99	36.17	54.38	4.38	78.23
724.27	31.25	43.46	-0.74	0.18	1.55	1.02	36.45	53.78	4.18	82.28
698.91	32.92	45.86	-0.77	0.17	1.61	1.06	36.64	53.22	4.00	83.30
673.75	34.72	48.44	-0.80	0.16	1.70	1.13	37.00	52.27	3.87	84.75
638.25	37.32	52.16	-0.83	0.15	1.79	1.16	38.58	50.21	3.69	86.68
604.82	39.95	55.98	-0.86	0.13	1.86	1.21	39.11	49.24	3.45	87.82
583.64	41.75	58.54	-0.89	0.11	1.90	1.24	40.72	47.36	3.40	89.86
569.74	43.51	61.05	-0.94	0.11	1.96	1.25	40.63	47.21	3.32	91.62

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Separation characteristics of nitric acid type tin stripping waste solution and distillation enhanced recovery of meta stannic acid

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溶液质量/g	总蒸失率/%	水蒸出率/%	pH	w（Sn⁴⁺）/ %	w（Fe³⁺）/ %	w（Cu²⁺）/ %	w（HNO₃）/ %	w（H₂O）/ %	w（馏出液的硝酸）/%	锡的析出率/%
1 891.08	0.00		-0.71	0.75	1.08	0.72	22.00	68.89	0.00	0.00
1 772.89	7.98	10.49	-0.61	0.42	1.16	0.76	24.04	67.35	9.35	47.50
1 656.43	12.92	17.27	-0.64	0.34	1.23	0.82	25.17	68.42	7.88	63.68
1 562.20	18.52	25.11	-0.67	0.20	1.32	0.86	27.33	66.18	6.59	77.53
1 513.30	20.08	27.32	-0.70	0.19	1.36	0.89	26.92	66.43	6.28	79.94
1 483.88	20.43	27.77	-0.73	0.17	1.39	0.90	25.90	67.37	6.36	82.53
1 448.08	24.97	34.33	-0.76	0.16	1.43	0.92	30.05	63.15	5.27	83.97
1 410.59	27.16	37.46	-0.79	0.15	1.46	0.95	31.08	61.94	4.95	85.18
1 356.28	27.85	38.44	-0.82	0.14	1.52	0.99	29.14	63.48	4.89	86.42
1 289.17	32.08	44.59	-0.85	0.14	1.62	1.02	31.56	60.58	4.23	87.37
1 223.38	36.42	50.75	-0.91	0.08	1.70	1.08	34.75	57.32	4.00	93.19
1 191.22	37.75	52.64	-0.94	0.06	1.75	1.11	35.22	56.82	3.93	95.13
1 175.23	38.57	53.79	-0.97	0.05	1.76	1.14	35.51	56.32	3.90	95.77
1 131.61	40.14	56.08	-1.00	0.05	1.84	1.17	35.64	55.86	3.73	95.93
1 086.73	41.91	58.66	-1.03	0.05	1.93	1.20	36.01	55.06	3.56	96.17
1 056.08	43.90	61.53	-1.06	0.05	1.98	1.24	37.61	53.12	3.41	96.35
1 001.16	45.90	64.42	-1.09	0.04	2.08	1.32	37.97	52.28	3.30	97.04
976.44	47.53	66.77	-1.12	0.04	2.13	1.36	39.73	50.46	3.20	97.18
960.01	48.22	67.75	-1.19	0.04	2.15	1.40	40.06	49.99	3.18	97.36

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